Additives for lubricants

ABSTRACT

The present invention relates to a composition containing a lubricant or hydraulic fluid and in an effective amount to improve extreme pressure and anti-wear properties of said lubricant or hydraulic fluid of at least one compound of the formula II ##STR1## R 1 , R 2 , and R 3  together with the C atom to which they are bound are tert-C 4  -C 14  -alkyl. R 4  is phenyl, --CH 2  --CH 2  --NH 2 , --CH 2  CH 2  OH, --CH 2  CH(OH)--CH 2  --OH, tert-C 4  -C 14  alkyl, --(CH 2 ) 2  --S--CH(OH)--CH 2  --S-(tert-C 8  -C 12  alkyl), --CH 2  --COOH, --CH 2  --COO--(i-C 8  H 17 ), --CH 2  --CO--OH.H 2  N-(tert-C 10  -C 16  -alkyl), --P(S)--[O--(i-C 3  H 7 )] 2 , --P(S)--[O--(i-C 8  H 17 )] 2 , α-naphthyl, benzothiazolyl, benzimidazolyl, thiazolyl, --CH 2  --CH--(OH)--CH 2  --S--R 10  wherein R 10  is tertiary C 4  -C 14  -alkyl, or R 4  is radical ##STR2## R 1 , R 2  and R 3  have the meaning defined above and R 11  is --(CH 2 ) 2  --O--(CH 2 ) 2  --O--(CH 2 ) 2  --, o-phenylene, thiadiazol-2,5-ylene or --(CH 2 ) u  --, u being zero to 2.

This application is a continuation of Ser. No. 07/999,173, filed Dec.28, 1992, abandoned, which is a continuation of Ser. No. 07/825,437,filed Jan. 23, 1992, abandoned, which is a continuation of Ser. No.07/717,163, filed Jun. 17, 1991, abandoned, which is a continuation ofSer. No. 07/107,896, filed Oct. 9, 1987, abandoned, which is acontinuation of Ser. No. 07/023,939, filed Mar. 5, 1987, abandoned,which is a continuation of Ser. No. 06/894,460, filed Jul. 30, 1986,abandoned, which is a continuation of Ser. No. 06/750,839, filed Jul. 1,1985, abandoned.

The present invention relates to lubricants and hydraulic fluids whichcontain compounds having thioether groups, to the use of these compoundsas additives, and to compounds having thioether groups.

Mercaptans, thioethers, di- and polysulfides and their use as lubricantadditives are known from the U.S. Pat. No. 4,246,127.

Various additives are in general added to lubricants to improve theperformance characteristics of the lubricants. Since lubricants requirea high load-carrying capacity for transmitting large forces, there areadded to them so-called high-pressure and anti-wear additives, by virtueof which the wear-phenomena otherwise occurring are greatly reduced.When on the other hand oxygen and moisture for example simultaneouslyact on a metal surface, corrosion can occur, and it is for this reasonthat corrosion inhibitors are added to,prevent these substances havingaccess to the metal surface. Oxidation reactions in a lubricantoccurring at elevated temperature to a greater extent as a result ofatmospheric oxygen can for example be inhibited by the addition ofantioxidants. It is known that certain substances, used as additives forlubricants, can combine a number of such properties and are hence knownas "multipurpose additives". Such substances are obviously in greatdemand for economic and practical reasons.

The compounds of this invention combine some of these properties.

The present invention relates also to compositions containing alubricant or a hydraulic fluid and at least one compound of the formulaI ##STR3## in which R can be a radical of the form ##STR4## wherein R¹,R² and R³ independently of one another are each C₅ -C₁₈ -alkyl andtogether contain no more than 22 C atoms, and R² and R³ are in additionhydrogen, or wherein R is C₅ -C₆ -cycloalkyl, phenyl or naphthylunsubstituted or substituted by C₁ -C₄ -alkyl), or is benzyl, furyl,thienyl, morpholinyl, imidazolyl, thiazolyl, oxazolyl, imidazolinyl,thiazolinyl, oxazolinyl, benzimidazolinyl, benzthiazolinyl orbenzoxazolinyl, and wherein R⁴ is phenyl unsubstituted or substituted by--NH₂, or is C₁ -C₁₆ -alkyl which is unsubstituted or substituted byphenyl, --NH₂, 2-oxo-pyrrolidino, cyano, perfluoro-C₁ -C₈ -alkyl or oneor two OH groups, and which can be interrupted by --O--or --S--, or isC₅ -C₆ -cycloalkyl, or R⁴ is .paren open-st.CH₂ .paren close-st._(m)S--CH₂ --CH(OH)--CH₂ --S--(C₁ -C₁₆ -alkyl), m being zero to 6, or R⁴ is.paren open-st.CH₂ .paren close-st._(n) C(O)--O--R⁵ wherein n is 1 or 2,and R⁵ is hydrogen, C₁ -C₁₆ -alkyl or an alkali metal, or wherein R⁴ is--CH[--CO--OR⁵ ][--CH₂ --CO--OR⁵ ] wherein R⁵ has the meaning givenabove, or wherein R⁴ is .paren open-st.CH₂ .paren close-st._(r)C(O)--OH.H₂ N--(C₈ -C₁₆ -alkyl) or .paren open-st.CH₂ .parenclose-st._(r) C(O)--OH.N.paren open-st.CH₂ --CH₂ --OH)₃, r being 1 or 2,or is --P(X).brket close-st.O--R⁶ ]₂, wherein X can be either ═O or ═S,and R⁶ is C₁ -C₁₆ -alkyl, phenyl or tolyl, or wherein R⁴ is α- orβ-naphthyl, benzothiazolyl, benzimidazolyl, benzoxazolyl, thiazolyl,thiazolinyl, triazolyl, tetrazolyl, pyridyl, quinolyl, imidazolyl,imidazolinyl, oxazolinyl, --SO₂ --O--(alkali metal), --C₆ H₄--C(O)--O--(alkali metal), 2-oxo-4-hydroxy-3-penten-3-yl or .parenopen-st.CH₂ .paren close-st._(s) R⁷, wherein s is 1 to 4, and R⁷ isbenzoxazolyl, benzimidazolyl, benzothiazolyl, thiazolinyl, imidazolinylor oxazolinyl, or wherein R⁴ is .paren open-st.CH₂ .paren close-st._(t)CO--N(R⁸)(R⁹), wherein t is 1 or 2, and R⁸ is C₁ -C₁₆ -alkyl which canbe substituted by --OH, or is phenyl, hydroxyphenyl or α-naphthyl, andR⁹ is hydrogen or R⁸ or wherein R⁴ is --CH₂ --CH(OH)--CH₂ --S--R¹⁰,wherein R¹⁰ is hydrogen or C₁ -C₁₆ -alkyl, or wherein R⁴ is a radical--R¹¹ --S--CH₂ --CH(OH)--CH₂ --S--R wherein R has the meaning givenabove, and R¹¹ is a radical .paren open-st.(CH₂ .paren close-st.₂O.paren open-st.(CH₂ .paren close-st.₂ O.paren open-st.(CH₂ .parenclose-st.₂, o -- or m-phenylene, thiadiazol-2,5-ylene or .parenopen-st.CH₂ .paren close-st._(u), u being zero to 8, or a radical of theformula ##STR5##

When R is a radical of the form ##STR6## it can be R¹ --CH₂ --, ##STR7##wherein R¹, R² and R³ are each C₁ -C₁₈ -alkyl. For C₁ -C₁₈ -alkyl, thesubstituents are straight-chain or branched-chain, for example: methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,straight-chain or branched-chain pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl or octadecyl. The preferred radical is ##STR8## wherein R¹,R² and R³ together with the C atom to which they are bound form C₄ -C₂₀-alkyl, and none of the substituents R¹, R² R³ may be hydrogen.Particularly preferred is C₄ -C₁₄ -alkyl, and especially preferred istert-butyl, tert-nonyl (ex Phillips Petroleum) or tert-dodecyl, bytert-dodecyl being meant for example a radical such as is described fortertiary dodecylmercaptan in "Ullmanns Enzyklopadie der technischenChemie, 4th Edition, Vol. 23, pp. 181-182, Verlag Chemie Weinheim".

When R is C₅ -C₆ -cycloalkyl, it is cyclopentyl or cyclohexyl.

If R is phenyl or naphthyl substituted by C₁ -C₄ -alkyl, the phenyl ornaphthyl can be mono- to trisubstituted, preferably howevermonosubstituted; C₁ -C₄ -alkyl is: methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl or tert-butyl.

R⁴ is C₁ -C₁₆ -alkyl, or when a C₁ -C₁₆ -alkyl radical is contained inthe substituents for R⁴, such as in: .paren open-st.CH₂ .parenclose-st._(m) --S--CH₂ --CH(OH)--CH₂ --S--(C₁ -C₁₆ -alkyl), .parenopen-st.CH₂ .paren close-st._(n) C(O)--O--(C₁ -C₁₆ -alkyl), --P(X).brketopen-st.O--R]₂ or --CH₂ --CH(OH)--CH₂ --S--(C₁ -C₁₆ -alkyl), or in thesubstituents for R⁵, R⁸ or R¹⁰, the radicals concerned arestraight-chain or branched-chain alkyl radicals, for example: methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, orstraight-chain or branched-chain pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl;preferred radicals are isopropyl, tert-butyl, isooctyl, 2-ethylhexyl,tert-nonyl, tert-dodecyl and tert-tridecyl. By isooctyl here is meant aradical which is derived from isooctyl alcohol, and which is a mixtureof differently branched octyl radicals. The definitions already givenabove apply for tert-nonyl as well as for tert-dodecyl.

When the meaning of R₄ is .paren open-st.CH₂ .paren close-st._(r)--C(O)--OH.H₂ N--(C₈ -C₁₆ -alkyl, the C₈ -C₁₆ -alkyl therein is astraight-chain or branched-chain substituent, for example: octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl,the preferred substituent being tert-tridecyl. Suitable as an amine ismoreover N.paren open-st.CH₂ --CH₂ --OH)₃.

If R⁴ is C₁ -C₁₆ -alkyl substituted by phenyl, it is preferably C₁ -C₄-alkyl substituted by phenyl, the phenyl being in the terminal position;and benzyl is particularly preferred.

When R⁴ is C₁ -C₁₆ -alkyl substituted by one or two OH groups, it ispreferably --CH₂ --CH₂ --OH, --CH(OH)--CH₂ --OH or --CH₂ --CH(OH)--CH₂--OH.

And when R⁴ is C₁ -C₁₆ -alkyl substituted by --NH₂, it is preferably--CH₂ --CH₂ --NH₂.

If R⁵ is an alkali metal, or if the latter occurs in --SO₂ --O--(alkalimetal) or in --C₆ H₄ --CO--O--(alkali metal), it is preferably sodium orpotassium.

Preferred compositions are those containing a lubricant or a hydraulicfluid and at least one compound of the formula II ##STR9## wherein R¹,R² and R³ together with the C atom to which they are bound are C₄ -C₂₀-alkyl, and none of these substituents R¹, R² and R³ may be hydrogen,and wherein R⁴ is phenyl unsubstituted or substituted by --NH₂, or is C₁-C₁₆ -alkyl which is unsubstituted or substituted by phenyl, --NH₂,2-oxopyrrolidino, cyano, perfluoro-C₁ -C₈ -alkyl or one or two OHgroups, and which can be interrupted by --O-- or --S--, or is C₅ -C₆-cycloalkyl, or R⁴ is .paren open-st.CH₂ .paren close-st._(m) S--CH₂--CH(OH)--CH₂ --S--(C₁ -C₁₆ -alkyl), m being zero to six, or .parenopen-st.CH₂ .paren close-st._(n) C(O)--O--R⁵, wherein n is 1 or 2, andR⁵ is hydrogen, C₁ -C₁₆ -alkyl or an alkali metal, or wherein R⁴ is--CH[--CO--OR⁵ ][--CH₂ --CO--OR⁵ ], wherein R⁵ has the meaning definedabove, or wherein R⁴ is .paren open-st.CH₂ .paren close-st._(r)C(O)--OH.H₂ N--(C₈ -C₁₆ -alkyl) or .paren open-st.CH₂ .parenclose-st._(r) C(O)--OH.N.paren open-st.CH₂ --CH₂ --OH)₃, r being 1 or 2,or is --P(X)∃O--R⁶ ]₂, wherein X can be either ═O or ═S, and R⁶ is C₁-C₁₆ -alkyl, phenyl or tolyl, or wherein R⁴ is α- or β-naphthyl,benzothiazolyl, benzimidazolyl, benzoxazolyl, thiazolyl, thiazolinyl,pyridyl, quinolyl, imidazolinyl, oxazolinyl, --SO₂ --O--(alkali metal),C₆ H₄ --C(O)--O--(alkali metal), 2-oxo-4-hydroxy-3-penten-3-yl, or.paren open-st.CH₂ .paren close-st._(s) R⁷, wherein s is 1 to 4, and R⁷is benzoxazolyl, benzimidazolyl, benzothiazolyl, thiazolinyl,imidazolinyl or oxazolinyl, or wherein R⁴ is .paren open-st.CH₂ .parenclose-st._(t) CO--N(R⁸)(R⁹), wherein t is 1 or 2 , and R⁸ is C₁ -C₁₆-alkyl which can be substituted by --OH, or is phenyl, 3-hydroxyphenylor α-naphthyl, and R is hydrogen or R⁸ or wherein R⁴ is --CH₂--CH(OH)--CH₂ --S--R¹⁰, wherein R¹⁰ is hydrogen or C₁ -C₁₆ -alkyl, orwherein R⁴ is a radical ##STR10## wherein R¹, R² and R³ have themeanings defined above, and R¹¹ is a radical .paren open-st.CH₂ .parenclose-st.₂ O.paren open-st.(CH₂ .paren close-st.₂ O.paren open-st.(CH₂.paren close-st.₂, o-- or m-phenylene, thiadiazol-2,5-ylene or .parenopen-st.CH₂ .paren close-st._(u), u being zero to 8, preferably 2, or aradical of the formula ##STR11##

Particularly preferred are compounds containing a lubricant or ahydraulic fluid and at least one compound of the formula II in which R¹,R² and R³ together with the C atom to which they are bound are C₄ -C₂₀-alkyl, and none of these substituents R¹, R² and R³ may be hydrogen,and wherein R⁴ is phenyl unsubstituted or substituted by --NH₂, or is C₁-C₁₃ -alkyl which is unsubstituted or substituted by phenyl, --NH₂,2-oxopyrrolidino, cyano or one or two OH groups, and which can beinterrupted by --O-- or --S--, or wherein R⁴ is .paren open-st.CH₂.paren close-st._(m) S--CH₂ --CH(OH)--, CH₂ --S--(C₁ -C₁₆ -alkyl), mbeing zero to 4, or is .paren open-st.(CH₂ .paren close-st._(n)CO--O--R⁵, wherein R⁵ is hydrogen, potassium or C₄ -C₁₂ -alkyl, and n is1 or 2, or wherein R⁴ is .paren open-st.CH₂ .paren close-st._(r)CO--OH.H₂ N--(C₁₀ -C₁₆ -alkyl), r being 1 or 2, or is --P(S).brketclose-st.O--R⁶ ]₂, wherein R⁶ is C₁ -C₈ -alkyl or phenyl, or wherein R⁴is α-naphthyl, thiazolyl, benzothiazolyl, benzimidazolyl, benzoxazolyl,pyridyl, quinolyl or .paren open-st.CH₂ .paren close-st._(s) R⁷ whereins is 1 or 2, and R⁷ it benzoxazolyl, benzimidazolyl, benzothiazolyl,thiazolinyl, imidazolinyl or oxazolinyl, or wherein R⁴ is .parenopen-st.CH₂ .paren close-st._(t) CO--(R⁸) (R⁹), wherein t is 1 or 2, andR⁸ is C₁ -C₄ -alkyl unsubstituted or substituted by --OH, or is phenylor α-naphthyl, and R⁹ is hydrogen or R⁸ or wherein R⁴ is --CH₂--CH(OH)--CH₂ --S--R¹⁰, wherein R¹⁰ is C₁ -C₁₄ -alkyl, or wherein R⁴ isa radical ##STR12## in which R¹, R² and R³ have the meanings definedabove and R¹¹ is --(CH₂)₂ --O--(CH₂)₂ --O--(CH₂)₂ --, o-- orm-phenylene, thiadiazol-2,5-ylene or .paren open-st.CH₂ .parenclose-st._(u), u being zero to 4, preferably 2.

More especially preferred are compounds containing a lubricant or ahydraulic fluid and at least one compound of the formula II in which R¹,R² and R³ together with the C atom to which they are bound are C₄ -C₁₄-alkyl, and none of these substituents R¹, R² and R³ may be hydrogen,and wherein R⁴ is phenyl, --CH₂ --CH₂ --NH₂, --CH₂ --CH₂ --OH, --CH₂--CH(OH)--CH₂ --OH, tertiary C₄ -C₁₄ -alkyl, --(CH₂)₂ --S--CH(OH)--CH₂--S--(tert-C₈ -C₁₂ -alkyl), --CH₂ --COOH--, CH₂ --CO--O--(i-C₈ H₁₇),--CH₂ --CO--OH.H₂ N--(tert-C₁ -C₁₆ -alkyl), --P(S).brketclose-st.O--(i-C₃ H₇)]₂, --P(S).brket close-st.O--(i-C₈ H₁₇)]₂,α-naphthyl, benzothiazolyl, benzimidazolyl, thiazolyl or --CH₂--CH(OH)--CH₂ --S--R¹⁰, wherein R¹⁰ is tertiary C₄ -C₁₄ -alkyl, orwherein R⁴ is a radical ##STR13## wherein R¹, R² and R³ have themeanings defined above, and R¹¹ is --(CH₂)₂ --o--(CH₂)₂ --O--(CH₂)₂ --,o-phenylene, thiadiazol-2,5-ylene or .paren open-st.CH₂ .parenclose-st._(u), u being zero to 2.

Further subject matter of the present invention is formed by novelsubstances of the formula II in which R¹, R² and R³ together with the Catom to which they are attached are C₄ -C₂₀ -alkyl, and none of thesesubstituents R¹, R² and R³ may be hydrogen, and wherein R⁴ --NH₂, or issubstituted by --NH₂, or is unsubstituted C₁ -C₉ -alkyl, or C₁ -C₁₆-alkyl which is substituted by phenyl, --NH₂, 2-oxopyrrolidino, cyano,perfluoro-C₁ -C₈ -alkyl or one or two OH groups, and which can beinterrupted by --O-- or --S--, or wherein R⁴ is .paren open-st.CH₂.paren close-st._(m) S--CH₂ --CH(OH)--CH₂ --S--(C₁ -C₁₆ -alkyl), m beingzero to 6 or is .paren open-st.CH₂ .paren close-st._(n) C(O)--O--R⁵,wherein n is 1 or 2, and R⁵ is hydrogen, C₁ -C₁₆ -alkyl or an alkalimetal, or wherein R⁴ is --CH[--CO--OR⁵ ][--CH₂ --CO--OR⁵ ], wherein R⁵has the meaning defined above, or wherein R⁴ is .paren open-st.CH₂.paren close-st._(r) C(O)--OH.H₂ N--(C₈ -C₁₆ -alkyl) or .parenopen-st.CH₂ .paren close-st._(r) C(O)--OH.N(--CH₂ --OH)₃, r being 1 or2, or is --P(X).brket close-st.O--R⁶ ]₂, wherein X can be either ═O or═S, and R⁶ is C₁ -C₁₆ -alkyl, phenyl or tolyl, or wherein R⁴ is α- orβ-naphthyl, benzothiazolyl, benzimidazolyl, benzoxazolyl, thiazolyl,thiazolinyl, pyridyl, quinolyl, imidazolinyl, oxazolinyl, --SO₂--O--(alkali metal), --C₆ H₄ --C(O)--O--(alkali metal) ,2-oxo-4-hydroxy-3-penten-3-yl or .paren open-st.CH₂ .paren close-st._(s)R⁷, wherein s is 1 to 4, and R⁷ is benzoxazolyl, benzimidazolyl,benzothiazolyl, thiazolinyl, imidazolinyl or oxazolinyl, or wherein R⁴is .paren open-st.CH₂ .paren close-st._(t) CO--N(R⁸)(R⁹), wherein t is 1or 2, and R⁸ is C₁ -C₁₆ -alkyl which is unsubstituted or substituted by--OH, or is phenyl, 3-hydroxyphenyl or α-naphthyl, and R⁹ is hydrogen orR⁸, or wherein R⁴ is --CH₂ --CH(OH)--CH₂ --S--R¹⁰, wherein R¹⁰ ishydrogen or C₁ -C₁₆ -alkyl or wherein R⁴ is a radical ##STR14## whereinR¹, R² R³ and have the meanings defined above, and R¹¹ is a radical.paren open-st.CH₂ .paren close-st.₂ O.paren open-st.CH₂ .parenclose-st.₂ O.paren close-st.CH₂ O .paren open-st.CH₂ .paren close-st.₂,o-- or m-phenylene, thiadiazol-2,5-ylene or .paren open-st.CH₂ .parenclose-st._(u), u being zero to 8, or a radical of the formula ##STR15##

Preferred compounds of the formula II are those wherein R¹, R² and R³together with the C atom to which they are bound are C₄ -C₂₀ -alkyl, andnone of these substituents R¹, R ² and R³ may be hydrogen, and whereinR⁴ is phenyl unsubstituted or substituted by --NH₂, unsubstituted C₄ -C₉-alkyl, or C₁ -C₁₃ -alkyl which is substituted by phenyl, --NH₂,2-oxopyrrolidino, cyano or one or two OH groups, or is .parenopen-st.CH₂ .paren close-st._(m) S--CH₂ --CH(OH)--CH₂ --S--(C₁ -C₁₆-alkyl), m being zero to 4, or is .paren open-st.CH₂ .parenclose-st._(n) CO--O--R⁵, R⁵ is hydrogen potassium or C₄ -C₁₂ -alkyl, andn is 1 or 2, or wherein R⁴ is .paren open-st.CH₂ .paren close-st._(r)CO--OH.H₂ N(C₁₀ -C₁₆ -alkyl), r being 1 or 2, or is --P(S).parenopen-st.O--R⁶ ]₂, wherein R is C₁ -C₈ -alkyl or phenyl, or wherein R⁴ isα-naphthyl, thiazolyl, benzothiazolyl, benzimidazolyl benzoxazolyl or.paren open-st.CH₂ .paren close-st._(s) R⁷, wherein s is 1 or 2, and R⁷is benzoxazolyl, benzimidazolyl, benzothiazolyl, thiazolinyl,imidazolinyl or oxazolinyl, or wherein R⁴ is .paren open-st.CH₂ .parenclose-st._(t) CO--N(R⁸)(R⁹), wherein t is 1 or 2, and R⁸ is C₁ -C₄-alkyl which is unsubstituted or substituted by --OH, or is phenyl orα-naphthyl, and R⁹ is hydrogen or R⁸, or wherein R⁴ is --CH₂--CH(OH)--CH₂ --S--R¹⁰, wherein R¹⁰ is C₁ -C₁₄ -alkyl, or wherein R⁴ isa radical ##STR16## in which R¹, R² and R³ have the meanings definedabove, and R¹¹ is --(CH₂ .paren close-st.O--(CH₂ .paren close-st.₂O--(CH₂ .paren close-st.₂, o-- or m-phenylene, thiadiazol-2,5-ylene or.paren open-st.CH₂ .paren close-st._(u), u being zero to 4, preferably2,.

Particularly preferred compounds of the formula II are those wherein R¹,R² R³ and together with the C atom to which they are bound are C₄ -C-alkyl, and none of these substituents R¹, R² and R³ may be hydrogen,and wherein R⁴ is phenyl, --CH₂ --CH₂ --NH₂, --CH₂ --CH₂ --OH, --CH₂--CH(OH)--CH₂ --OH, tertiary C₄ -C₉ -alkyl, --(CH₂)₂ --S--CH₂--CH(OH)--CH₂ --S--(tert-C₈ -C₁₂ -alkyl), --CH₂ COOH, --CH₂--CO--O--(i-C₈ H₁₇), --CH₂ --CO--OH.H₂ N--(tert-C₁₀ -C₁₆ -alkyl),--P(S).brket close-st.O--(i-C₃ H₇)]₂, --P(S).brket close-st.O--(i-C₈H₁₇)]₂, α-naphthyl, benzothiazolyl, benzimidazolyl, thiazolyl or --CH₂--CH(OH)--CH₂ --S--R¹⁰, wherein R¹⁰ is tertiary C₄ -C₁₄ -alkyl orwherein R⁴ is a radical ##STR17## in which R¹, R² and R³ have themeanings defined above, and R¹¹ is --(CH₂)₂ --O--(CH₂)₂ --O--(CH₂)₂ --,o-phenylene, thiadiazol-2,5-ylene or .paren open-st.CH₂ .parenclose-st._(u), u being zero to 2.

The following are examples of compounds of the formula I: ##STR18##

The alkyl-thiaglycidyl ethers, used as intermediates for the compoundsof the formula I, are produced in the following manner: ##STR19##wherein the substituent R has the meanings already defined. Particularlyadvantageous for this reaction is the use of a phase-transfer catalyst,for example tetrabutylamine chloride. The production ofalkyl-thiaglycidyl ethers is described also in the Patent SpecificationsNos. U.S. Pat. No. 2,965,652, 2,731,437 and BE 609,375.

The compounds of the formula I can be produced by reaction ofalkyl-thiaglycidyl ethers of the formula III with a compound of theformula IV

    HS--R.sup.4                                                (IV),

with the use of catalytical amounts of nucleophiles, such as sodiumhydride or triethylamine, the substituents R and R⁴ having the meaningsalready defined.

Other methods suitable for the production of compounds of the formula Iare described for example in the German Offenlegungsschrift No.2,730,414.

Another method of synthesis comprises coupling the glycidylthioethersynthesis with the addition reaction of the same mercaptan: ##STR20##whereby some of the compounds embraced by the formula I can be produced.

A further method of synthesis proceeds by way of the following reaction:##STR21## to α-hydroxymercaptan derivatives which yield with chlorinecompounds Cl--R⁴ the desired compounds of the formula I, the cleavedhydrogen chloride being bound by an inorganic or organic base. Theoxidative coupling of α-hydroxy-mercaptan derivatives results moreoverin some compounds of the formula I being obtained with a disulfidestructure.

In addition, it is possible in the case of some compounds of the formulaI to use also the following method of synthesis: ##STR22## wherein --CH₂--CH₂ --R' can be a radical denoted specifically by R⁴.

Finally, an α-hydroxymercaptan compound of this kind can be reacted witha glycidyl ether, as shown by the example given below: ##STR23##

The compounds of the formula I are of a thinly liquid, viscous towax-like nature, and are surprisingly readily soluble in lubricants.They are particularly suitable as additives in lubricants, and result inan improvement of the high-pressure and anti-wear properties; to beemphasised also is their anti-oxidising and anticorrosive activity. Inconclusion, they render possible, surprisingly, the preparation ofso-called masterbatches.

The compounds of the formula I are effective even in very small amountsas additives in lubricants. They are added to the lubricants in anamount of 0.01 to 5% by weight, preferably 0.05 to 3% by weight,relative to the amount of lubricant. The lubricants concerned arefamiliar to a person skilled in the art, and are described for examplein "Lubricants and related Products" (Schmierstoffe und verwandteProdukte) [Verlag Chemie, Weinheim, 1982]. Particularly suitable,besides mineral oils, are for example poly-α-olefins, lubricants basedon esters; or phosphates, glycols, polyglycols and polyalkylene glycols.

The lubricants can additionally contain other additives which are addedto further improve the basic properties lubricants: such additivesinclude: antioxidants, metal passivators, rust inhibitors,viscosity-index improvers, pour-point depressors, dispersants,detergents, high-pressure additives and anti-wear additives.

Examples of phenolic antioxidants

1. Alkylated monophenols

2,6-di-tert-butyl-4-methylphenol,

2,6-di-tert-butylphenol,

2-tert-butyl-4,6-dimethylphenol,

2,6-di-tert-butyl-4-ethylphenol,

2,6-di-tert-butyl-4-n-butylphenol,

2,6-di-tert-butyl-4-i-butylphenol,

2,6-di-cyclopentyl-4-methylphenol,

2-(α-methylcyclohexyl)-4,6-dimethylphenol,

2,6-di-octadecyl-4-methylphenol,

2,4,6-tri-cyclohexylphenol,

2,6-di-tert-butyl-4-methoxymethylphenyl, and

o-tert-butylphenol.

2. Alkylated hydroquinones

2,6-di-tert-butyl-4-methoxyphenol,

2,5-di-tert-butyl-hydroquinone,

2,5-di-tert-amyl-hydroquinone, and

2,6-diphenyl-4-octadecyloxyphenol.

3. Hydroxylated thiodiphenyl ethers

2,2'-thio-bis(6-tert-butyl-4-methylphenol),

2,2'-thio-bis(4-octylphenol),

4,4'-thio-bis(6-tert-butyl-3-methylphenol), and

4,4'-thio-bis(6-tert-butyl-2-methylphenol).

4. Alkylidene bis phenols

2,2'-methylene-bis(6-tert-butyl-4-methylphenol),

2,2'-methylene-bis(6-tert-butyl-4-ethylphenol),

2,2'-methylene-bis[4-methyl-6-(α-methylcyclohexyl)phenol],

2,2'-methylene-bis(4-methyl-6-cyclohexylphenol),

2,2'-methylene-bis(6-nonyl-4-methylphenol),

2,2'-methylene-bis(4,6-di-tert-butylphenol),

2,2'-ethylidene-bis(4,6-di-tert-butylphenol),

2,2'-ethylidene-bis(6-tert-butyl-4-isobutylphenol),

2,2'-methylene-bis[6-(α-methylbenzyl)-4-nonylphenol],

2,2'-methylene-bis[6-(α,α-dimethylbenzyl)-4-nonylphenol],

4,4'-methylene-bis(2,6-di-tert-butylphenol),

4,4'-methylene-bis(6-tert-butyl-2-methylphenol),

1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane,

2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,

1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecyl-mercaptobutane,

ethylene glycol-bis[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate],

di- (3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene, and

di-[2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-4-methyl-phenyl]terephthalate.

5. Benzyl compounds

1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,

di-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,

3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetic acid isooctyl ester,

bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiolterephthalate,

1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,

1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,

3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid dioctadecyl ester, and

calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acidmonoethyl ester.

6. Acylaminophenols

4-hydroxylauric acid anilide,

4-hydroxystearic acid anilide,

2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4-hydroxy-anilino)-s-triazine,and

N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamic acid octyl ester.

7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmonohydric or polyhydric alcohols, for example with:

methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethyleneglycol diethylene glycol, triethylene glycol, pentaerythritol,trishydroxyethyl isocyanurate or dihydroxyethyloxalic acid diamide.

8. Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith monohydric or polyhydric alcohols, for example with:

methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,trishydroxyethyl isocyanurate or dihydroxyethyloxalic acid diamide.

9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, forexample:

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine,

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

10. Examples of amine antioxidants

N,N'-diisopropyl-p-phenylenediamine

N,N'-di-sec-butyl-p-phenylenediamine,

N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine,

N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,

N,N'-bis(1-methyl-heptyl)-p-phenylenediamine,

N,N'-dicyclohexyl-p-phenylenediamine,

N,N'-diphenyl-p-phenylenediamine,

N,N'-di(naphthyl-2-)-p-phenylenediamine,

N-isopropyl-N'-phenyl-p-phenylenediamine,

N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,

N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,

N-cyclohexyl-N'-phenyl-p-phenylenediamine,

4-(p-toluenesulfonamido)-diphenylamine,

N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,

4-isopropoxydiphenylamine,

N-phenyl-1-naphthylamine,

N-phenyl-2-naphthylamine,

octylated diphenylamine,

4-n-butylaminophenol,

4-butyrylaminophenol,

4-nonanoylaminophenol,

4-dodecanoylaminophenol,

4-octadecanoylaminophenol,

di-(4-methoxyphenyl)amine,

2,6-di-tert-butyl-4-dimethylaminomethylphenol,

2,4'-diaminodiphenylmethane,

4,4'-diaminodiphenylmethane,

N,N,N,N'-tetramethyl-4,4'-diaminodiphenylmethane,

1,2-di(phenylamino)ethane,

1,2-di-[(2-methylphenyl)-amino]ethane,

1,2-di(phenylamino)propane,

(o-tolyl)biguanide,

di-[4-(1', 3'-dimethylbutyl)phenyl)amine, tert-octylatedN-phenyl-1-naphthylamine, and mixture of mono- and dialkylatedtert-butyl/tert-octyldiphenylamines.

Examples of metal passivators are:

for copper, for example: benzotriazole, tetrahydrobenzotriazole,2-mercaptobenzotriazole, 2,5-dimercaptothiadiazole,salicylidene-propylenediamine and salts of salicylaminoguanidene.

Examples of rust inhibitors are:

a) organic acids, the esters thereof, metal salts and anhydridesthereof, for example: N-oleylsarcosine, sorbitan monooleate, leadnaphthenate, dodecenylsuccinic acid anhydride, alkenylsuccinic acidhalf-ester and 4-nonylphenoxyacetic acid;

b) nitrogen-containing compounds, for example:

I. primary, secondary or tertiary aliphatic or cycloaliphatic amines andamine salts of organic and inorganic acids, for example oil-solublealkylammonium carboxylates;

II. heterocyclic compounds, for example: substituted imidazolines andoxazolines;

c) phosphorus-containing compounds, for example: amine salts ofphosphoric acid partial esters;

d) sulfur-containing compounds, for example: bariumdinonylnaphthalenesulfonates and calcium petroleum sulfonates.

Examples of viscosity-index improvers are for example:

polymethacrylate, vinyl pyrrolidone/methacrylate copolymers,polybutenes, olefin copolymers and styrene/acrylate copolymers.

Examples of pour-point depressors are for example:

polymethacrylates and alkylated naphthalene derivatives.

Examples of dispersants/surfactants are for example:

polybutenylsuccinimides, polybutenylphosphonic acid derivatives, basicmagnesium, calcium and barium sulfonates and phenolates.

Examples of anti-wear additives are for example:

compounds containing sulfur and/or phosphorus and/or halogen, such assulfurised vegetable oils, zinc dialkyldithiophosphates,tritolylphosphate, chlorinated paraffins and alkyl- and aryldisulfides.

The compounds according to the invention are used as additives forlubricant systems, especially motor oils. In lubricant systems theyexhibit: high-pressure, antiwear, antioxidising and corrosion-inhibitingactivity. A particular advantage of these compounds, in contrast tocompounds having comparable properties, is that they are free fromphosphorus and tin, as a result of which the aftercombustion of theexhaust gases is also not impaired. Furthermore, these compounds do notcontain any hydrolytically or solvolytically clearable bonds and aretherefore also particularly stable.

The following Production Examples are given in order to furtherillustrate the invention, the Examples 1 to 3 concerning intermediatesfor producing the compounds of the formula I, and the Examples 4 to 41describing these compounds of the formula I.

EXAMPLE 1

(cf. Table 1) Tert-octylglycidyl thioether

A solution of 66 parts by weight of sodium hydroxide, 300 parts byweight of water and 8 parts by weight of tetrabutylammonium chloride isadded dropwise at 15° to 20° C. in the course of 70 minutes, withstirring and partial cooling (especially at the commencement of theaddition), to a mixture of 219 parts by weight of tert-octylmercaptanand 135 parts by weight of epichlorohydrin. The reaction mixture isfurther stirred for 1 hour at 50° C.; the aqueous phase is thenseparated, and the organic phase is washed with 200 parts by weight ofwater. The organic phase is finally distilled in vacuo to thus obtainthe tert-octylglycidyl thioether in the form of a colourless liquidhaving a boiling point of 74° to 75° C. at 0.02 mbar, and a refractiveindex of n_(D) ²⁰ =1.4803; the yield is 250 parts by weight, whichcorresponds to 82% of the theoretical yield.

EXAMPLE 4

(cf. Table 1):

27.1 parts by weight of tert-dodecylglycidyl thioether are addeddropwise at 50°-60° C., with stirring, to a mixture of 7.8 parts byweight of 2-mercaptoethanol and catalytical amounts of sodium hydride(exothermic reaction). After completion of the addition, stirring iscontinued at the same temperature for 1 hour, and the following compoundis thus obtained as a yellow viscous liquid having a refractive index ofn_(D) ²⁰ =1.5132 in a yield of 100%. ##STR24##

EXAMPLES 2 AND 3 AND 5-41:

Compounds 2 and 3 (Examples 2 and 3) are prepared by a method analogousto that of Example 1, and compounds 5 to 41 are prepared by a methodanalogous to that of Example 4.

                                      TABLE 1                                     __________________________________________________________________________                                                        Physical data             Ex-                                                 Boiling                   ample                                               point                     No. Formula                                  Observations                                                                         (°C.)                                                                         n.sub.D.sup.20     __________________________________________________________________________         ##STR25##                               colourless liquid                                                                     74-75° C./ at                                                         2.66                                                                                 1,4803             2                                                                                  ##STR26##                               colourless liquid                                                                     81-82° C./ at                                                         1.33                                                                                 1,4800             3                                                                                  ##STR27##                               colourless liquid                                                                    100-102° C./                                                           at 1.33                                                                              1,4800             4                                                                                  ##STR28##                               viscous liquid                                                                              1,5132             5                                                                                  ##STR29##                               viscous liquid                                                                              1,5115             6                                                                                  ##STR30##                               viscous liquid                                                                              1,4958             7                                                                                  ##STR31##                               viscous liquid                                                                              1,4905             8                                                                                  ##STR32##                               viscous liquid                                                                              1,5331             9                                                                                  ##STR33##                               viscous liquid                                                                              1,5210             10                                                                                 ##STR34##                                                                11                                                                                 ##STR35##                               viscous liquid                                                                              1,5049             12                                                                                 ##STR36##                                             1,5056             13                                                                                 ##STR37##                               viscous liquid                                                                              1,5650             14                                                                                 ##STR38##                               viscous liquid                                                                              1,4982             15                                                                                 ##STR39##                               viscous liquid                                                                              1,5590             16                                                                                 ##STR40##                               colourless liquid                                                                           1,5221             17                                                                                 ##STR41##                               colourless liquid                                                                    133-135° C./                                                           at 2.66                                                                              1,5010             18                                                                                 ##STR42##                               viscous liquid                                                                              1,5112             19                                                                                 ##STR43##                               viscous liquid                                                                              1,5298             20                                                                                 ##STR44##                               colourless liquid                                                                           1,5590             21                                                                                 ##STR45##                               viscous liquid                                                                              1,5908             22                                                                                 ##STR46##                               colourless liquid                                                                     88-92° C./ at                                                         3.99                                                                                 1,4961             23                                                                                 ##STR47##                               colourless liquid                                                                    143-147° C./                                                           at 6.65                                                                              1,4990             24                                                                                 ##STR48##                                      168-169° C./                                                           at 2.66                                                                              1,5392             25                                                                                 ##STR49##                                      160-161° C. at                                                         5.32                                                                                 1,5477             26                                                                                 ##STR50##                                             1,5638             27                                                                                 ##STR51##                                             1,5446             28                                                                                 ##STR52##                                       97-98° C. at                                                          5.32                                                                                 1,5000             29                                                                                 ##STR53##                                             1,4179             30                                                                                 ##STR54##                                             1,5467             31                                                                                 ##STR55##                                             1,5845             32                                                                                 ##STR56##                                             1,5491             33                                                                                 ##STR57##                               solid substance                                                                      melting point                                                                 46-48°             34                                                                                 ##STR58##                                             1,5160             35                                                                                 ##STR59##                                             1,5122             36                                                                                 ##STR60##                                             1,5224             37                                                                                 ##STR61##                                             1,5143             38                                                                                 ##STR62##                                      153-156° C. at                                                         6.65                                                                                 1,4948             39                                                                                 ##STR63##                                             1,5170             40                                                                                 ##STR64##                                             1,5830             41                                                                                 ##STR65##                                             1,561              __________________________________________________________________________

The following Application Example serves to further illustrate theresults obtained by application of additives according to the presentinvention.

Application Example 1

With the Shell four-ball apparatus (IP 239/73--Extreme pressure and wearlubricant test for oils and greases four-ball machine), the followingvalues are obtained:

1. W.L.=Weld Load: this is the load under which the 4 balls weldtogether within 10 seconds.

2. W.S.D.=Wear Scar Diameter in mm.: this is the mean wear diameter witha load of 400N during 60 minutes.

A basic oil having a viscosity of ISO-VH 100 with a low content ofaromatic compounds and containing 0.035% of S is used as the test fluidfor determining the effectiveness of the additives.

                  TABLE 2                                                         ______________________________________                                                Test with the Shell four-ball apparatus                               Additive  W.L. (N)        W.S.D. (mm)                                         Example No.                                                                             1% of    2.5% of    0.25% of                                                                             1.0% of                                  (cf. Table 1)                                                                           additive additive   additive                                                                             additive                                 ______________________________________                                        4         2200     2400       0.60   0.50                                     5         1800                       0.75                                     6         2200     2400       0.60   0.50                                     7         1800                       0.75                                     8         2200     2400       0.50   0.50                                     9         2200     2200       0.50   0,70                                     10        2200     2600       0.70   0,75                                     11        2200     2400       0.50   0,50                                     12        2200     2400       0.50   0,50                                     13        2000     2200       0.50   0.50                                     16        2000     2200       0.55   0.60                                     17        2000     2400       0.50   0.55                                     19        2200     2400       0.60   0,65                                     20        2400     2800       0.55   0,65                                     21        2350     2700                                                       22        2000     2200       0.50   0,55                                     23        2000     2050                                                       ______________________________________                                    

What is claimed is:
 1. A composition containing a lubricant or hydraulicfluid and in an effective amount to improve extreme pressure andanti-wear properties of said lubricant or hydraulic fluid of at leastone compound of the formula II ##STR66## which R¹, R², and R³ togetherwith the C atom to which they are bound are tert-C₄ -C₁₄ -alkyl, andnone of these substituents R¹, R² and R³ may be hydrogen, and wherein R⁴is phenyl, --CH₂ --CH₂ --NH₂, --CH₂ CH₂ OH, --CH₂ CH(OH)--CH₂ --OH,tert-C₄ -C₁₄ alkyl, --(CH₂)₂ --S--CH(OH)--CH₂ --S--(tert-C₈ -C₁₂ alkyl),--CH₂ --COOH, --CH₂ --COO--(i-C₈ H₁₇), --CH₂ --CO--OH.H₂ N--(tert-C₁₀-C₁₆ -alkyl), --P(S)--[O--(i-C₃ H₇)]₂, --P(S)--[O--(i-C₈ H₁₇)]₂,α-naphthyl, benzothiazolyl, benzimidazolyl, thiazolyl, --CH₂--CH--(OH)--CH₂ --S--R¹⁰ is wherein R¹⁰ is tertiary C₁ -C.sub. -alkyl,tertiary C₄ -C₁₄ -alkyl, ##STR67## wherein R¹, R² and R³ have themeaning defined above, and R¹¹ is --(CH₂)₂ --O--(CH₂)₂ --O--(CH₂)₂ --,o-phenylene, thiadiazol-2,5-ylene or --(CH₂)_(u) --, u being zero to 2.2. A composition according to claim 1, containing a lubricant or ahydraulic fluid and at least one compound of the formula II in which uis 0 and R⁴ is --R¹¹ --S--CH₂ --CH(OH)CH₂ --S--tert-octyl.
 3. Acomposition according to claim 1, containing a lubricant or a hydraulicfluid and at least one compound of the formula II in which u is 0 and R⁴is --R¹¹ --S--CH₂ --CH(OH)CH₂ --S--tert-nonyl.
 4. A compositionaccording to claim 1, containing a lubricant or a hydraulic fluid and atleast one compound of the formula II in which u is 0 and R⁴ is --R¹¹--S--CH₂ --CH(OH)CH₂ --S--tert-butyl.
 5. A composition according toclaim 1, containing a lubricant or a hydraulic fluid and at least onecompound of the formula ##STR68##
 6. A process for improving thehigh-pressure and anti-wear properties of a lubricant or hydraulic fluidby incorporating therein an effective amount of at least one compound offormula II according to claim 1.